Prepreg compositions, their manufacture, and determination of their suitability for use in composite structures

ABSTRACT

A prepreg composition includes a plurality of core/shell quantum dots that exhibit an increase in detectable luminescence when the prepreg composition has been exposed to an amount of UV radiation that would render the prepreg composition unsuitable for use in fabricating composite structures, thereby greatly simplifying detection of compromised prepreg materials that for example, may have been inadvertently and undesirably exposed to UV radiation during storage or handling. A method of manufacturing a prepreg composition includes forming a bed of fibers, contacting the fiber bed with a resin matrix, and disposing a plurality of core/shell quantum dots on or in the resin matrix.

FIELD

This disclosure relates to the manufacture of composite materials, andmore specifically to the manufacture of pre-impregnated composite fibermaterials, or prepreg.

BACKGROUND

Composite materials may be used in a wide variety of industries,particularly in applications where strength, stiffness, and decreasedweight are desirable. In some applications, the manufacturing processmay be simplified and/or streamlined through the use of prepreg.

Prepreg refers to intermediate materials that include “pre-impregnated”composite fibers, or fibers bound in a matrix material such as a resin.In prepreg, however, the matrix is only partially cured to allow easyhandling. This B-Stage material may require cold storage in order toslow and/or prevent complete curing of the matrix. However, while heatmay accelerate polymerization of pre-preg material, exposure toultraviolet (UV) radiation may also result in an undesirable degree ofpremature polymerization.

UV light can be generated from many sources, such as the sun, standardflorescent lights, mercury lamps, hydrogen lamps, and xenon arc lamps.Unfortunately, UV light can have a significant effect on carbon-basedmaterials such as reinforced plastics, and in particular on uncuredresins that may be used in the manufacture of composite materials.

As a result, some prepreg may be given a projected useful lifetime basedupon an estimated exposure of the prepreg to known or suspected sourcesof UV radiation. Unfortunately, such calculated lifetimes may notreflect actual UV exposure, resulting in the use of potentiallyunsuitable materials in manufacture, or may actually overestimate UVexposure, resulting in the wasteful and unnecessary discarding of costlymaterials.

SUMMARY

The present disclosure provides prepreg compositions methods ofmanufacturing prepreg compositions, and methods for determining thesuitability of a prepreg composition for use in fabricating compositestructures.

In some embodiments, the disclosure may provide methods of manufacturinga prepreg composition, comprising forming a bed of fibers, contactingthe fiber bed with a resin matrix, and disposing a plurality ofcore/shell quantum dots on or in the resin matrix. The core/shellquantum dots of the method may include an inner core covered by an outershell, the inner core being configured such that when it is excited bylight of a first wavelength the inner core emits a detectableluminescent signal at a second wavelength, while the outer shell may beconfigured to substantially block light of the first wavelength fromreaching the inner core when the outer shell is intact. The outer shellmay be further configured so that exposing the outer shell to athreshold amount of UV radiation may result in sufficient degradation ofthe outer shell that the inner core may emit the detectable luminescentsignal when the quantum dot is illuminated by light having the firstwavelength, where the threshold amount of UV radiation is that amountthat is sufficient to render the prepreg composition unsuitable for usein fabricating composite structures.

In some embodiments, the disclosure may provide a prepreg compositionthat includes a bed of fibers disposed in a resin matrix, and aplurality of core/shell quantum dots. The quantum dots may comprise aninner core covered by an outer shell, the inner core being configuredsuch that when excited by light of a first wavelength the inner coreemits a detectable luminescent signal at a second wavelength, and wherethe outer shell is configured to substantially block light of the firstwavelength from reaching the inner core when the outer shell is intact.The quantum dot outer shell may be further configured so that exposureto a threshold amount of UV radiation results in sufficient degradationthat the inner core emits the detectable luminescent signal when thequantum dot is illuminated by light at the first wavelength, where thethreshold amount of UV radiation is the amount sufficient to render theprepreg composition unsuitable for use in fabricating compositestructures.

In some embodiments, the disclosure may provide a method of determiningthe suitability of a prepreg composition for incorporation into acomposite structure, where the prepreg composition comprises a bed offibers disposed in a resin matrix, and a plurality of core/shell quantumdots disposed on or in the resin matrix. Each quantum dot may include aninner core covered by an outer shell, where the inner core is configuredso that when it is excited by light at a first wavelength the inner coreemits a detectable luminescent signal at a second wavelength, and anouter shell that is configured to substantially block light of the firstwavelength from reaching the inner core when the outer shell is intact.The outer shell may be further configured to degrade upon exposure to UVradiation, so that a detection of the luminescent signal at the secondwavelength indicates that the quantum dot has been exposed to UVradiation. The method includes illuminating the prepreg composition withlight of the first wavelength, detecting the luminescent signal at thesecond wavelength from the quantum dots, and determining a suitabilityof the prepreg composition for incorporation in a composite structurebased upon at least the detected luminescent signal at the secondwavelength.

The features, functions, and advantages may be achieved independently invarious embodiments of the present disclosure, or may be combined in yetother embodiments, further details of which can be seen with referenceto the following description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic depiction of an illustrative core/shell quantumdot exposed to both UV radiation and radiation having a firstwavelength.

FIG. 2 is a schematic depiction of the illustrative core/shell quantumdot of FIG. 1 , showing degradation of the outer shell by exposure to UVradiation.

FIG. 3 is a schematic depiction of the illustrative core/shell quantumdot of FIG. 1 , showing the illumination of the inner core by radiationhaving a first wavelength, and the emission of radiation having a secondwavelength.

FIG. 4 is a flowchart depicting an illustrative method of manufacturinga pre-impregnated composite material that comprises core/shell quantumdots.

FIG. 5 is a schematic depiction of an illustrative apparatus fordetecting the exposure of a prepreg composition to UV radiation.

FIG. 6 is a schematic depiction of an alternative illustrative apparatusfor detecting the exposure of a prepreg composition to UV radiation.

FIG. 7 is a flowchart depicting an illustrative method of determiningthe suitability of a prepreg composition for incorporation into acomposite structure.

FIG. 8 is a flowchart depicting an illustrative method of determiningbenchmark value for luminescence emission of a core/shell quantum dotstandard.

DESCRIPTION Overview

Various embodiments of a pre-impregnated composite materials thatincorporate core/shell quantum dots are described below and illustratedin the associated drawings. Unless otherwise specified, thepre-impregnated composite materials and/or their various components may,but are not required to, contain at least one of the structure,components, functionality, and/or variations described, illustrated,and/or incorporated herein. Furthermore, the structures, components,functionalities, and/or variations described, illustrated, and/orincorporated herein in connection with the present teachings may, butare not required to, be included in other similar composite materials.The following description of various embodiments is merely exemplary innature and is in no way intended to limit the disclosure, itsapplication, or uses. Additionally, the advantages provided by theembodiments, as described below, are illustrative in nature and not allembodiments provide the same advantages or the same degree ofadvantages.

Quantum Dots

Quantum dots typically refer to nanoclusters, or nanoparticles, of asemiconducting material, so called because they may have diameters inthe range of 2-10 nanometers. Quantum dots may display unique electronicand optical properties, including luminescence. Generally, as the sizeof the quantum dot decreases, the luminescence emission shifts fromlonger wavelength to shorter wavelengths. As a result, quantum dots canbe tuned during manufacturing to emit any color of light by altering thesize and/or composition of the nanoparticles.

The efficiency and brightness of such semiconductor quantum dots may beenhanced by applying a shell of another, higher band gap semiconductingmaterial around the nanocluster. Quantum dots having a semiconductingmaterial embedded within another having a wider band gap may be known ascore/shell quantum dots (CSQDs) or core/shell semiconductingnanocrystals (CSSNCs).

Examples, Components, and Alternatives

The following examples describe selected aspects of exemplary prepregcompositions, their components, their manufacture, and/or theircharacterization. These examples are intended for illustration andshould not be interpreted as limiting the entire scope of the presentdisclosure. Each example may include one or more distinct inventions,and/or contextual or related information, function, and/or structure.

Example 1

This example describes an illustrative core/shell quantum dot for use inan exemplary prepreg composition. As shown in FIG. 1 , core/shellquantum dot 10 includes an inner core 12 surrounded by an outer shell14. The composition and/or size of the core and shell may be tailored toproduce a quantum dot that exhibits desired optical properties.

The core/shell quantum dots of the present disclosure may be selectedand/or configured so that the quantum dots exhibit a detectable opticalresponse when exposed to an amount of UV radiation considered sufficientto render the resin matrix of an associated prepreg compositionunsuitable for use in fabricating composite structures. A detectableoptical response generally comprises a change in, or an occurrence of,an optical signal that is detectable by direct visual observation and/orby suitable instrumentation. Typically, the detectable optical responseis a change in a spectral property of the quantum dot, such as a changein absorbance or a change in luminescence. Such changes may includechanges in wavelength and/or intensity. Where the detectable opticalresponse is a detectable luminescence response, the changes may includechanges in the intensity, polarization, lifetime, and/or excitation oremission wavelength distribution of the luminescence, among others. Forexample, a condition of interest or change in condition may be measuredas the appearance of increase of sample luminescence. In oneillustrative example, the core/shell quantum dots of the presentdisclosure may be selected and/or configured so that the quantum dotsexhibit a detectable luminescent response when exposed to an amount ofUV radiation determined to be sufficient to render the resin matrix ofan associated prepreg composition unsuitable for incorporation in acomposite structure.

For example, a core/shell quantum dot 10 may be prepared or selected topossess photophysical properties such that the inner core 12 of quantumdot 10 is capable of being excited by light having a selected firstwavelength 16, and that after excitation, the core 12 may then emitluminescence at a second wavelength 18.

The outer shell 14 of quantum dot 10 may be prepared or selected so thatit is at least substantially not excited by light having a firstwavelength 16, and so at least substantially nonluminescent at thesecond wavelength 18 upon illumination by light 16. However, outer shell14 may be configured to absorb ultraviolet (UV) wavelengths of radiation20, and to undergo degradation when exposed to UV radiation 20. In oneillustrative embodiment, the absorbance spectrum of the outer shell 14is configured to at least partially match the absorbance spectrum of aresin used in manufacturing prepreg compositions, particularly in ornear the UV region.

In FIG. 1 , quantum dot 10 is intact, including outer shell 14, and evenupon illumination by light of a first wavelength 16 the quantum dot issubstantially nonluminescent. However, upon illumination of quantum dot10 with UV radiation 20 the outer shell 14 begins to degrade, as shownin FIG. 2 . Upon additional exposure to UV radiation, outer shell 14will degrade sufficiently that light having a first wavelength 16 mayreach inner core 12.

As shown in FIG. 3 , once outer shell 14 is degraded sufficiently, lighthaving the first wavelength 16 can reach and therefore can excite theinner core 12, thereby stimulating a luminescence emission at a secondwavelength 18.

The amount of UV radiation exposure that is needed before illuminationof quantum dot 10 at the first wavelength results in a detectableemission at the second wavelength may be considered to correspond to anamount of UV radiation sufficient to degrade outer shell 14. It shouldbe appreciated that while the detection of an emission at the secondwavelength may confirm the exposure of the quantum dot 10 to sufficientUV radiation to degrade outer shell 14, it does not necessarily providean indication of the intensity of the UV radiation. That is, sufficientUV radiation may be attained through cumulative exposure to a relativelylow level of illumination, or sufficient UV radiation may be attainedvia a brief but energetic exposure.

Suitable and illustrative core/shell quantum dots for the purposes ofthis disclosure may incorporate an inner core that may include one ormore of InP, CdSe, CdSeS, CdTe, ZnS, and ZnO, among others. Theillustrative core/shell quantum dots may incorporate an outer shell thatmay include one or more of CdS, ZnSe, and ZnS, among others. Methods ofsynthesizing, characterizing, and modifying the optical properties ofquantum dots have been well described. For example, a variety ofCdSe/ZnS core/shell quantum dots have been prepared and characterizedpreviously (see Dabbousi et al. J. Phys. Chem. B 1997, 101, 9463-9475;van Embden et al. Langmuir, 2005 21, 10226-10233).

Example 2

This example describes a method of manufacturing a pre-impregnatedcomposite material that comprises core/shell quantum dots. FIG. 4 is aflowchart 30 illustrating operations performed in an illustrativemethod, and may not recite the complete process or all steps of theprogram. Flowchart 30 depicts multiple steps of a method ofmanufacturing a pre-impregnated composite material, and although varioussteps of flowchart 30 are described below and depicted in FIG. 4 , thesteps need not necessarily all be performed, and in some cases may beperformed in a different order than the order shown.

The manufacture of a pre-impregnated composite material, or prepreg, mayinclude forming a bed of fibers, at 32 of flowchart 30.

The fibers used to form the fiber bed may be uniform or non-uniform, andmay have similar or different compositions. In some embodiments, thefibers may be polymer-based, including polyester polymers such aspolyethylene, or polyamide polymers such as poly-aramid, among others.The fibers may be derived from natural sources, such as plants, forexample flax, hemp, or agave, among others. The fibers may be or includeglass fibers or fused quartz fibers. The fibers may include filamentarycrystals. The fibers may include continuous fibers of refractorycompounds. The fibers may include asbestos fibers, beryllium fibers,beryllium carbide fibers, or beryllium oxide fibers. The fibers mayinclude boron fibers or boron nitride fibers. In one illustrativeexample the fibers may include carbon fibers, such as graphite fibers.The fibers may include woven fibers or non-woven fibers.

The fiber bed, once formed, is then contacted with a resin matrix, at 34of flowchart 30. The resin matrix may include a thermoset resin. Inparticular, the resin matrix may include one or more of an epoxy resin,a phenolic resin, a polyester resin, a polyurethane resin, a vinyl esterresin, and a bismaleimide resin.

The manufacture of the composite material includes disposing a pluralityof core/shell quantum dots on or in the resin matrix. In oneillustrative example, the plurality of quantum dots is disposed on or inthe resin matrix prior to contacting the fiber bed with the resinmatrix, at 36 of flowchart 30. In order for the quantum dots to serve asuseful indicators of UV exposure, the quantum dots may be disposed at ornear the surface of the resin. Provided that sufficient quantum dotsoccur at or near the surface of the resulting prepreg, this may be asatisfactory method of incorporating the quantum dots into the resin.

Alternatively, the plurality of quantum dots is disposed on or in theresin matrix after the resin contacts the fiber bed, at 38 of flowchart30. This may result in a greater percentage of the plurality of quantumdots localizing at or near a surface of the resin matrix, and thereforeremaining accessible to UV radiation exposure.

In one illustrative embodiment of the disclosure, the plurality ofquantum dots is disposed on a surface of a prepreg composition, andadheres to the surface either due to the inherent stickiness of thepartially cured resin matrix, or through the application of an adhesive.

Alternatively, the plurality of quantum dots may be disposed on acarrier that is configured to be, in turn, attached to a surface of aprepreg composition. The carrier may, for example, include an adhesivebacking to facilitate attachment. The carrier may therefore assume thefunctionality of a label, or sticker, that can be adhered to a surfacein such a way that the outward-facing surface of the carrier includesthe plurality of quantum dots.

It should be appreciated that the utility of the core/shell quantum dotsof the present disclosure in indicating an exposure to UV radiation neednot be limited to prepreg compositions, but could be useful in detectingUV exposure of a wide range of materials. In particular, where theplurality of core/shell quantum dots is disposed on a carrier, thecarrier may be readily attached to any surface or object in order tofacilitate the detection of an exposure of that surface or object to UVradiation.

Example 3

This example describes an apparatus for evaluating suitability ofprepreg for the manufacture of composite structures.

FIG. 5 is a schematic depiction of a detection apparatus 40. Thedetection apparatus 40 may be configured to employ changes in theoptical properties of the core/shell quantum dots disclosed herein toevaluate a prepreg composition, and in particular may be configured toemploy the luminescence properties of the core/shell quantum dots toevaluate a prepreg composition.

Luminescence-based analytical methods may involve (1) exposing a sampleto a condition capable of inducing luminescence from the sample, and (2)observing a detectable luminescence response, where the luminescenceresponse is indicative of a condition of interest.

The detectable luminescence response generally comprises a change in, oran occurrence of, a luminescence signal that is detectable by directvisual observation and/or by suitable instrumentation. Typically, thedetectable response is a change in a property of the luminescence, suchas a change in the intensity, polarization, lifetime, and/or excitationor emission wavelength distribution of the luminescence. For example, acondition of interest or a change in a condition of interest may bemeasured as the appearance of increase of sample luminescence.

The detectable response may be simply detected, or it may be quantified.A response that is simply detected generally comprises a response whoseexistence merely is confirmed, whereas a response that is quantifiedgenerally comprises a response having a quantifiable (e.g., numericallyreportable) value such as an intensity, polarization, and/or otherproperty.

Scanning apparatus 40 may include an excitation source 42, and adetector 44. Excitation source 42 may be any light source capable ofexciting the inner core of the core/shell quantum dot present in theprepreg composition. The prepreg may be excited by a light sourcecapable of producing light at or near a wavelength of peak absorption ofthe inner core, such as for example anan arc lamp, a fluorescent bulb,or even an incandescent bulb. The prepreg may be excited with lighthaving a wavelength within 20 nm of the maximum absorption of the innercore of the quantum dot, although excitation by a source more alignedwith maximum absorption band of the inner core may result in highersensitivity. Excitation sources may include, for example, fixed,hand-held, or movable lamps, including mercury arc lamps and xenonlamps, and laser light sources such as argon-ion lasers, diode lasers,and Nd-YAG lasers, among others.

The detectable luminescence response of the quantum dot present in or onthe resin matrix of the prepreg may be detected qualitatively, oroptionally quantitatively. The luminescence response is typicallydetected by the human eye by simple observation, or by a detector 44that may include one or more of a CCD camera, a video cameras,photographic film, or other light-sensing apparatus. Detector 44 may beoperatively coupled with a computer 46 that may be configured to storeand/or analyze the data obtained by detector 44.

As shown in FIG. 5 , detection apparatus 40 may be stationary withrespect to a prepreg composition 50, or it may scan the surface of theprepreg 50. Scanning may be accomplished by translating one or both ofthe excitation source 42 and detector 44 along prepreg 50, or by using apivoting or rotating mirror 48 to scan the prepreg while the detectorremains stationary.

As shown in FIG. 6 , the detection apparatus 40 may alternatively, oradditionally, include a scanning excitation source 42 and a plurality ofdetectors 44 operatively coupled to a computer 46. Using such anapparatus, an image of an entire surface of a prepreg composition may bedetected and/or recorded at once. In this way, localized luminescencepatterns may be detected, which may identify particular areas of concernand/or help identify the source of stray UV light that may compromisethe prepreg during storage.

Example 4

This example describes a method of determining a suitability of prepregfor incorporation into a composite structure. As discussed above,prepreg may include a fiber bed incorporated into a resin matrix.Typically, the resin matrix of the prepreg is at least partially cured,and may be cured to the B-stage. The curing process of a prepreg may behalted at the B-stage, by cooling the prepreg at the appropriateintermediate stage of curing.

Once it is partially cured, even when the prepreg may be kept at lowtemperatures to prevent further curing, accidental and/or unavoidableexposure to UV radiation may cause additional curing of the resin. Thisadditional curing may render the prepreg unsuitable for use infabricating a composite material. For example, unwanted additionalcuring may compromise the ability of the resin to flow under heat andpressure, resulting in unsatisfactory compaction during incorporation ofthe prepreg into a composite structure and an unsuitable compositestructure.

A prepreg may be considered suitable for fabrication of a compositestructure when the prepreg resin retains enough capacity for furthercuring that the resin component of the prepreg will flow under appliedheat and/or pressure. More specifically, a prepreg may be consideredsuitable for fabrication of a composite structure when the prepregretains sufficient capacity for further curing that the prepregundergoes adequate compaction during autoclaving, and the compositestructure incorporating the prepreg satisfies the quality controlstandards for that structure.

A prepreg may be considered unsuitable for fabrication of a compositestructure when the prepreg has undergone sufficient additional curingthat the prepreg fails to exhibit adequate flow and/or compaction evenduring autoclaving. Alternatively or in addition, a prepreg may beconsidered unsuitable when a composite structure incorporating theprepreg fails to meet the quality control standards for that compositestructure.

A standard test may be used to evaluate the resin flow characteristicsof a prepreg, in order to evaluate suitability of that prepreg. Forexample, ASTM International has established a standard test methodologyfor evaluating the amount of resin flow that will occur for a givenprepreg tape or sheet under defined conditions of temperature andpressure (see ASTM Intel. Test Method D3531/D3531M-11, herebyincorporated by reference). The core/shell quantum dots of the presentdisclosure may be tailored to generate a luminescent signal afterexposure to an amount of UV radiation correlating to a desired level ofchange in resin flow characteristics, as measured by such a standardtest method. It should be appreciated that through appropriate designand synthesis, a core/shell quantum dot may be prepared that wouldindicate a change in resin flow characteristics of, for example, 2%, 5%,10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, or more.

Alternatively, or in addition, a standard test may be used to evaluatethe tensile strength of a prepreg material, or a composite structurefabricated from a prepreg material, and the exposure of the prepregmaterial to UV radiation may be correlated with a loss of strength orintegrity of the resulting composite structure, as determined by astandard tensile or pull-test. In this instance, the core/shell quantumdots of the present disclosure may be tailored to generate a luminescentsignal when the prepreg has been exposed to an amount of UV radiationcorrelating to a target decrease in tensile strength, as measured by astandard tensile or pull-test, for example, a decrease of 2%, 5%, 10%,20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, or more.

FIG. 7 includes flowchart 70 of operations performed in an illustrativemethod of determining the suitability of a prepreg for incorporationinto a composite structure. Flowchart 70 may not recite the completeprocess or all steps of the process, and although various steps offlowchart 70 are described below and depicted in FIG. 7 , the steps neednot necessarily all be performed, and in some cases may be performed ina different order than the order shown.

The method depicted by flowchart 70 includes determining the suitabilityof a prepreg for incorporation into a composite structure, where theprepreg composition comprising a bed of fibers disposed in a resinmatrix, and that includes a plurality of core/shell quantum dots asdescribed above. At 72 of flowchart 70, the prepreg composition isilluminated with light of the first wavelength. At 74, the luminescentsignal generated by the quantum dots at the second wavelength isdetected. At 76, the suitability of the prepreg composition forincorporation in a composite structure is determined, based upon atleast the detected luminescent signal at the second wavelength.

In one aspect of the method, the core/shell quantum dots are selectedsuch that the detection of any luminescence signal at the secondwavelength may be sufficient to make a determination that the prepreghas been compromised by exposure to UV radiation, and that theincorporation of that prepreg into a composite structure may negativelyimpact the strength, stability, lifetime, or other characteristic of thecomposite structure. That is, the core/shell quantum dots are configuredsuch that an amount of UV exposure sufficient to degrade the outer shellof the quantum dot and expose the inner core to the UV radiation hasbeen experimentally and/or theoretically determined to be a sufficientamount of UV exposure to render a prepreg composition incorporating thequantum dot unsuitable for use. As shown at 76, based upon the detectedluminescent signal, a determination that the prepreg is not suitable forfurther use may result in discarding the prepreg, at 78. Alternatively,the absence of a detectable luminescent signal at the second wavelengthmay be used to indicate that the prepreg remains suitable for use inmanufacturing the desired composite structure.

Optionally, the detectable luminescent response may be quantified, at80, where quantification may correspond to determining the intensity, ormagnitude, of the luminescence response in a systematic way. Accuratequantification of the luminescence response may be enhanced bycalibration of detector 44 and/or computer 46 before, during, or afterthe luminescent signal at the second wavelength is detected.

Once the luminescence response is quantified, the quantified signal maybe correlated with exposure of the prepreg to UV radiation, at 72. Sucha correlation may be performed by comparison of the detected and/orrecorded luminescence response to a prepared luminescence standard or toa standard curve. For example, the measured luminance response may becompared with that obtained from a standard composition of a knownconcentration of quantum dots in a known composition of prepreg, havingbeen exposed to a known amount of UV radiation. Alternatively, or inaddition, a standard curve may be prepared, using variable exposure of atest sample to increasing intensity and/or duration of UV exposure andrecording the resulting luminescence response, so that the quantifiedluminescent signal may be used to interpolate a value for the amount ofUV radiation to which the prepreg may have been exposed.

Also optionally, and as shown at 74 of flowchart 60, the amount ofexposure of the prepreg to UV radiation may be further correlated withthe degree of curing such an exposure may create within the resinmatrix. Again, such correlation may require the creation of a standardcurve.

FIG. 8 illustrates a flowchart 90 of an illustrative method of obtaininga benchmark luminescence emission, where the benchmark luminescenceemission may be used in conjunction with the process of flowchart 70 todetermine the suitability of a prepreg composition for incorporationinto a composite structure.

In order to determine how much UV radiation exposure will result in aprepreg that is unsuitable for further use, a threshold amount of UVradiation may be determined, at 92 of flowchart 90. The threshold amountof UV radiation is that amount sufficient to render a prepregcomposition unsuitable for use in fabricating a composite structure,typically due to excessive curing of the resin. This threshold value maybe determined theoretically, or may be determined empirically throughtesting.

Once the threshold amount of UV radiation is determined, a standard orcontrol sample of core/shell quantum dots as discussed above are exposedto the threshold amount of UV radiation, at 94. After such exposure, thesample of core/shell quantum dots is then illuminated with light of thefirst wavelength, at 96. The resulting luminescence emission of thequantum dots is measured, at 98. This measured luminescence correspondsto a benchmark luminescence. That is, the benchmark luminescence is thatamount of luminescence that, when generated by the quantum dots in aprepreg compositions, may be correlated with an exposure of the prepregcomposition to the threshold amount of UV radiation. More simply, wherea prepreg composition is illuminated by light of the first wavelengthand generates the benchmark level of luminescence at the secondwavelength, the prepreg composition may therefore be consideredunsuitable for incorporation into a composite structure.

Example 5

This section describes additional aspects and features of the prepregcompositions of the present disclosure, their manufacture, and theirevaluation, presented without limitation as a series of paragraphs, someor all of which may be alphanumerically designated for clarity andefficiency. Each of these paragraphs can be combined with one or moreother paragraphs, and/or with disclosure from elsewhere in thisapplication, including the materials incorporated by reference in theCross-References, in any suitable manner. Some of the paragraphs belowexpressly refer to and further limit other paragraphs, providing withoutlimitation examples of some of the suitable combinations. Each of theparagraphs including the term “substantially” may also be provided inthe same form excepting that the term “substantially” is deleted.

-   A0. A method of manufacturing a prepreg composition, comprising:-   forming a bed of fibers;-   contacting the fiber bed with a resin matrix; and-   disposing a plurality of core/shell quantum dots on or in the resin    matrix.-   A1. The method of paragraph A0, wherein the plurality of core/shell    quantum dots exhibit a detectable optical response when exposed to    an amount of UV radiation sufficient to render the prepreg    composition unsuitable for use in fabricating composite structures.-   A2. The method of paragraph A1, wherein each quantum dot includes an    inner core covered by an outer shell, the inner core being    configured such that when excited by light of a first wavelength the    inner core emits a detectable luminescent signal at a second    wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured such that exposure to a        threshold amount of UV radiation results in sufficient        degradation that the inner core emits the detectable luminescent        signal when the quantum dot is illuminated by light having the        first wavelength;    -   wherein the threshold amount of UV radiation is the amount        sufficient to render the prepreg composition unsuitable for use        in fabricating composite structures.-   A2a. The method of paragraph A1, wherein each quantum dot includes    an inner core covered by an outer shell, the inner core being    configured such that when excited by light of a first wavelength the    inner core emits a detectable luminescent signal at a second    wavelength;    -   the outer shell being configured to block light of the first        wavelength from reaching the inner core when the outer shell is        intact; and    -   the outer shell being further configured such that exposure to a        threshold amount of UV radiation results in sufficient        degradation that the inner core emits the detectable luminescent        signal when the quantum dot is illuminated by light having the        first wavelength;    -   wherein the threshold amount of UV radiation is the amount        sufficient to render the prepreg composition unsuitable for use        in fabricating composite structures.-   A3. The method of paragraph A0, wherein contacting the fiber bed    with a resin matrix includes contacting the fiber bed with a    thermoset resin.-   A4. The method of paragraph A0, wherein the plurality of core/shell    quantum dots are disposed on or in the resin matrix before the resin    matrix contacts the fiber bed.-   A5. The method of paragraph A0, wherein the plurality of core/shell    quantum dots are disposed on or in the resin matrix after the resin    matrix contacts the fiber bed.-   A6. The method of paragraph A2 or A2a, wherein the outer shell is    configured so that exposing the outer shell to UV radiation does not    result in a detectable luminescent signal that substantially    overlaps with the second wavelength.-   A7. The method of paragraph A2 or A2a, wherein the outer shell is    configured so that exposing the outer shell to UV radiation does not    result in a detectable luminescent signal.-   A8. The method of paragraph A0, where partially curing the prepreg    composition includes curing the prepreg composition to B-stage.-   A9. The method of paragraph A0, where partially curing the prepreg    composition includes cooling the prepreg composition to stop the    curing process.-   A10. The method of paragraph A0, further comprising storing the    partially cured prepreg composition in cold storage.-   A11. The method of paragraph A0, where the fiber bed includes woven    fibers.-   A12. The method of paragraph A0, where the fiber bed includes    non-woven fibers.-   A13. The method of paragraph A0, where the plurality of core/shell    quantum dots includes double shell or triple shell quantum dots.-   B0. A prepreg composition comprising:-   a bed of fibers disposed in a resin matrix; and-   a plurality of core/shell quantum dots disposed on or in a partially    cured resin matrix;    -   wherein the plurality of core/shell quantum dots exhibit a        detectable optical response when exposed to an amount of UV        radiation sufficient to render the prepreg composition        unsuitable for use in fabricating composite structures.-   B1. The prepreg composition of paragraph B0, wherein each quantum    dot includes an inner core covered by an outer shell, the inner core    being configured such that when excited by light of a first    wavelength the inner core emits a detectable luminescent signal at a    second wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured to degrade upon        exposure to UV radiation such that detection of the luminescent        signal at the second wavelength indicates that the quantum dot        has been exposed to UV radiation;    -   wherein at least some of the quantum dots are at or on a resin        surface and accessible to illumination.-   B2. The prepreg composition of paragraph B0, where the prepreg    composition is cured to B-stage.-   B3. The prepreg composition of paragraph B0, where the resin matrix    includes a thermoset resin.-   B4. The prepreg composition of paragraph B0, where the resin matrix    includes an epoxy resin, a phenolic resin, or a bismaleimide resin.-   B5. The prepreg composition of paragraph B0, where the bed of fibers    includes woven fibers.-   B6. The prepreg composition of paragraph B0, where the bed of fibers    includes non-woven fibers.-   C0. A resin composition, comprising:-   an uncured resin;-   a plurality of core/shell quantum dots dispersed in the resin    material;    -   where each quantum dot includes an inner core covered by an        outer shell, the inner core being configured such that when        excited by light of a first wavelength the inner core emits a        detectable luminescent signal at a second wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured to degrade upon        exposure to UV radiation such that detection of the luminescent        signal at the second wavelength indicates that the quantum dot        has been exposed to UV radiation.-   C1. The resin composition of paragraph C0, where the uncured resin    is an uncured thermoset resin.-   C2. The resin composition of paragraph C1, further comprising one or    more additives selected from among curing agents, hardeners,    tougheners, accelerators, and flame retardants.-   D0. A prepreg composition comprising:-   a bed of fibers disposed in a resin matrix; and-   a plurality of core/shell quantum dots; wherein the plurality of    core/shell quantum dots exhibit a detectable optical response when    exposed to an amount of UV radiation sufficient to render the resin    matrix unsuitable for use in fabricating composite structures.-   D1. The prepreg composition of paragraph D0, wherein each quantum    dot comprises an inner core covered by an outer shell, the inner    core being configured such that when excited by light of a first    wavelength the inner core emits a detectable luminescent signal at a    second wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured such that exposure to a        threshold amount of UV radiation results in sufficient        degradation that the inner core emits the detectable luminescent        signal when the quantum dot is illuminated by light having the        first wavelength;    -   wherein the threshold amount of UV radiation is an amount        sufficient to render the prepreg composition unsuitable for use        in fabricating composite structures.-   D1a. The prepreg composition of paragraph D0, wherein each quantum    dot comprises an inner core covered by an outer shell, the inner    core being configured such that when excited by light of a first    wavelength the inner core emits a detectable luminescent signal at a    second wavelength;    -   the outer shell being configured to block light of the first        wavelength from reaching the inner core when the outer shell is        intact; and    -   the outer shell being further configured such that exposure to a        threshold amount of UV radiation results in sufficient        degradation that the inner core emits the detectable luminescent        signal when the quantum dot is illuminated by light having the        first wavelength;    -   wherein the threshold amount of UV radiation is an amount        sufficient to render the prepreg composition unsuitable for use        in fabricating composite structures.-   D2. The composition of paragraph D0, wherein each core/shell quantum    dot has an inner core comprising one or more of InP, CdSe, CdSeS,    CdTe, ZnS, and ZnO; and an outer shell comprising one or more of    CdS, ZnSe, and ZnS.-   D3. The composition of paragraph D0, wherein each core/shell quantum    dot is a CdSe/ZnS core/shell quantum dot.-   D4. The prepreg composition of paragraph D1 or D1a, wherein the    outer shell is substantially nonluminescent at the second wavelength    when exposed to UV radiation.-   D4a. The prepreg composition of paragraph D1 or D1a, wherein the    outer shell is nonluminescent at the second wavelength when exposed    to UV radiation.-   D5. The prepreg composition of paragraph D1 or D1a, wherein the    outer shell is substantially nonluminescent when exposed to UV    radiation.-   D5a. The prepreg composition of paragraph D1 or D1a, wherein the    outer shell is nonluminescent when exposed to UV radiation.-   D6. The prepreg composition of paragraph D0, wherein the resin    matrix includes a thermoset resin.-   D7. The prepreg composition of paragraph D0, wherein the resin    matrix includes one or more of an epoxy resin, a phenolic resin, a    polyester resin, a polyurethane resin, a vinyl ester resin, and a    bismaleimide resin.-   D8. The prepreg composition of paragraph D0, wherein the bed of    fibers comprises at least one of woven fibers and non-woven fibers.-   D9. The prepreg composition of paragraph D0, wherein the bed of    fibers comprises one or more of synthetic polymer fibers and natural    fibers derived from plant sources.-   D10. The prepreg composition of paragraph D0, wherein the bed of    fibers comprises one or more of carbon fibers, boron fibers, and    boron nitride fibers.-   E0. A core/shell quantum dot, comprising:    -   an inner core covered by an outer shell, the inner core being        configured such that when excited by light of a first wavelength        the inner core emits a detectable luminescent signal at a second        wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured to degrade upon        exposure to UV radiation such that detection of the luminescent        signal at the second wavelength indicates that the quantum dot        has been exposed to UV radiation.-   E1. The quantum dot of paragraph E0, where the inner core/outer core    has a composition of CdS/ZnS, CdSe/ZnS, CdSe/CdS, or InAs/CdSe.-   E2. The quantum dot of paragraph EU, wherein the quantum dot is    disposed on a carrier that is configured to be attached to a    surface.-   E3. The quantum dot of paragraph E2, wherein the carrier is an    adhesive carrier configured to be adhered to the surface.-   F0. A method of determining a suitability of a prepreg composition    for incorporation into a composite structure, comprising:-   illuminating the prepreg composition with light of a first    wavelength, wherein the prepreg composition comprises    -   a plurality of core/shell quantum dots disposed on or in the        resin matrix, each quantum dot including an inner core covered        by an outer shell;        -   the inner core being such that when excited by light of the            first wavelength the inner core emits a detectable            luminescent signal at a second wavelength;        -   the outer shell being configured to substantially block            light of the first wavelength from reaching the inner core            when the outer shell is intact; and        -   the outer shell being further configured to degrade upon            exposure to UV radiation such that a detection of the            luminescent signal at the second wavelength indicates that            the quantum dot has been exposed to UV radiation;-   detecting the luminescent signal at the second wavelength from the    inner core; and-   determining a suitability of the prepreg composition for    incorporation in a composite structure based upon at least the    presence of the detected luminescent signal at the second    wavelength.-   F0a. A method of determining a suitability of a prepreg composition    for incorporation into a composite structure, comprising:-   illuminating the prepreg composition with light of a first    wavelength, wherein the prepreg composition comprises    -   a plurality of core/shell quantum dots disposed on or in the        resin matrix, each quantum dot including an inner core covered        by an outer shell;        -   the inner core being such that when excited by light of the            first wavelength the inner core emits a detectable            luminescent signal at a second wavelength;        -   the outer shell being configured to block light of the first            wavelength from reaching the inner core when the outer shell            is intact; and        -   the outer shell being further configured to degrade upon            exposure to UV radiation such that a detection of the            luminescent signal at the second wavelength indicates that            the quantum dot has been exposed to UV radiation;-   detecting the luminescent signal at the second wavelength from the    inner core; and-   determining a suitability of the prepreg composition for    incorporation in a composite structure based upon at least the    presence of the detected luminescent signal at the second    wavelength.-   F1. The method of paragraph F0 or F0a, further comprising:-   quantifying the detected luminescent signal; and-   correlating a magnitude of the quantified luminescent signal with an    amount of exposure of the prepreg composition to UV radiation.-   F2. The method of paragraph F1, wherein correlating the quantified    luminescent signal with the amount of exposure of the prepreg    composition to UV radiation includes comparing the quantified    luminescent signal with a benchmark luminescence emission;    -   wherein the benchmark luminescence emission is obtained by:        -   determining a threshold amount of UV radiation sufficient to            render the prepreg composition unsuitable for use in            fabricating the composite structure;        -   exposing a core/shell quantum dot standard to the threshold            amount of UV radiation;        -   illuminating the core/shell quantum dot standard with light            of the first wavelength; and        -   measuring the resulting benchmark luminescence emission.-   F3. The method of paragraph F0 or F0a, wherein illuminating the    prepreg composition includes illuminating a surface of the prepreg    composition with light of the first wavelength.-   F4. The method of paragraph F0 or F0a, where detecting the    luminescent signal at the second wavelength includes exposing a    surface of the prepreg composition to a detector.

F5. The method of paragraph F0 or F0a, wherein detecting the luminescentsignal at the second wavelength includes localizing the luminescentsignal on a surface of the prepreg composition.

-   G0. A method of detecting an exposure of a prepreg composition to UV    radiation, comprising:-   forming a prepreg composition that includes a bed of fibers and a    plurality of core/shell quantum dots bound in a partially cured    resin matrix, where    -   each quantum dot includes an inner core covered by an outer        shell, the inner core being configured such that when excited by        light of a first wavelength the inner core emits a detectable        luminescent signal at a second wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured to degrade upon        exposure to UV radiation such that detection of the luminescent        signal at the second wavelength indicates that the quantum dot        has been exposed to UV radiation;-   illuminating the prepreg composition with light of the first    wavelength;-   detecting a luminescent signal at the second wavelength from the    quantum dots;-   correlating the detected luminescent signal with exposure of the    prepreg composition to UV radiation.-   G1. The method of paragraph G0, further comprising:-   quantifying the detected luminescent signal; and-   correlating the quantified luminescent signal with an amount of    exposure of the prepreg composition to UV radiation.-   G2. The method of paragraph G1, further comprising:-   correlating the amount of exposure of the prepreg composition to UV    radiation with a suitability of the prepreg composition for    fabricating composite structures.-   G3. The method of paragraph G1, where illuminating the prepreg    composition includes scanning light of the first wavelength across    the surface of the prepreg composition.-   G4. The method of paragraph G3, where illuminating the prepreg    composition includes generating light of the first wavelength with    an excitation source.-   G5. The method of paragraph G4, where illuminating the prepreg    composition includes generating light of the first wavelength with    an excitation source that is a laser excitation source.-   G6. The method of paragraph G0, where detecting the luminescent    signal at the second wavelength includes using a detector sensitive    to light at the second wavelength.-   G7. The method of paragraph G6, where detecting the luminescent    signal at the second wavelength includes scanning across a surface    of the prepreg composition with the detector.-   G8. The method of paragraph G6, where detecting the luminescent    signal at the second wavelength includes exposing an entire surface    of the prepreg composition to the detector simultaneously.-   G9. The method of paragraph G6, where detecting the luminescent    signal includes using detector that includes a CCD or CMOS sensor.-   G10. The method of paragraph G6, where detecting the luminescent    signal at the second wavelength includes localizing the luminescent    signal on a surface of the prepreg composition.-   H0. A method of detecting exposure of a composition to UV radiation,    comprising:-   incorporating a plurality of core/shell quantum dots in or on the    composition, where    -   each quantum dot includes an inner core covered by an outer        shell, the inner core being configured such that when excited by        light of a first wavelength the inner core emits a detectable        luminescent signal at a second wavelength;    -   the outer shell being configured to substantially block light of        the first wavelength from reaching the inner core when the outer        shell is intact; and    -   the outer shell being further configured to degrade upon        exposure to UV radiation such that detection of the luminescent        signal at the second wavelength indicates that the quantum dot        has been exposed to UV radiation;-   illuminating the composition with light of the first wavelength;-   detecting a luminescent signal at the second wavelength from the    quantum dots;-   correlating the detected luminescent signal with exposure of the    composition to UV radiation.

Advantages, Features, Benefits

The different embodiments of prepreg compositions, their manufacture,and their evaluation described herein provide several advantages overknown solutions for addressing the degradation of prepreg due to UVexposure. More specifically, the presently described methods permit forfast and cost-effective characterization of UV exposure of compositematerials prior to manufacturing, potentially resulting in significantcost savings. In addition, the methods described herein may be appliedto any other industry or material where exposure to UV or otherradiation sources may compromise product quality.

CONCLUSION

The disclosure set forth above may encompass multiple distinctinventions with independent utility. Although each of these inventionshas been disclosed in its preferred form(s), the specific embodimentsthereof as disclosed and illustrated herein are not to be considered ina limiting sense, because numerous variations are possible. The subjectmatter of the inventions includes all novel and nonobvious combinationsand subcombinations of the various elements, features, functions, and/orproperties disclosed herein. The following claims particularly point outcertain combinations and subcombinations regarded as novel andnonobvious. Inventions embodied in other combinations andsubcombinations of features, functions, elements, and/or properties maybe claimed in applications claiming priority from this or a relatedapplication. Such claims, whether directed to a different invention orto the same invention, and whether broader, narrower, equal, ordifferent in scope to the original claims, also are regarded as includedwithin the subject matter of the inventions of the present disclosure.

What is claimed is:
 1. A prepreg composition comprising: a bed of fibersdisposed in a resin matrix, wherein the bed of fibers and resin matrixare suitable for fabricating composite structures until the bed offibers and resin matrix are exposed to a threshold amount of UVradiation; and a plurality of core/shell quantum dots disposed withinthe resin matrix, an inner core of each quantum dot being configured toemit a luminescent signal when excited by light, and an outer shellbeing configured to block light from reaching the inner core when theouter shell is intact; wherein the plurality of core/shell quantum dotsis configured such that exposure of the bed of fibers and resin matrixto the threshold amount of UV radiation results in emission of theluminescent signal when the plurality of core/shell quantum dots isilluminated.
 2. The composition of claim 1, wherein the inner core ofeach quantum dot is configured such that when excited by light of afirst wavelength the inner core emits the luminescent signal at a secondwavelength; and the outer shell of each quantum dot is furtherconfigured such that exposure to the threshold amount of UV radiationresults in sufficient degradation that the inner core emits theluminescent signal when the quantum dot is illuminated by light havingthe first wavelength.
 3. The prepreg composition of claim 2, wherein theouter shell is nonluminescent at the second wavelength when exposed toUV radiation.
 4. The prepreg composition of claim 2, wherein the outershell is nonluminescent when exposed to UV radiation.
 5. The compositionof claim 2, wherein the size and/or composition of the outer shell ofthe quantum dot is selected so that the outer shell blocks light of thefirst wavelength from reaching the inner core when the outer shell isintact, and exposure to the threshold amount of UV radiation results insufficient degradation of the outer shell that the inner core is exposedto illumination; and the size and/or composition of the inner core ofthe quantum dot is selected so that the inner core emits the luminescentsignal when illuminated by light having the first wavelength.
 6. Thecomposition of claim 1, wherein each core/shell quantum dot has an innercore comprising one or more of InP, CdSe, CdSeS, CdTe, ZnS, and ZnO; andan outer shell comprising one or more of CdS, ZnSe, and ZnS.
 7. Thecomposition of claim 1, wherein each core/shell quantum dot is aCdSe/ZnS core/shell quantum dot.
 8. The prepreg composition of claim 1,wherein the resin matrix includes a thermoset resin.
 9. The prepregcomposition of claim 1, wherein the resin matrix includes one or more ofan epoxy resin, a phenolic resin, a polyester resin, a polyurethaneresin, a vinyl ester resin, and a bismaleimide resin.
 10. The prepregcomposition of claim 1, wherein the bed of fibers comprises one or moreof synthetic polymer fibers, natural fibers derived from plant sources,carbon fibers, boron fibers, and boron nitride fibers.
 11. Thecomposition of claim 1, wherein the prepreg composition is B-stage. 12.The composition of claim 1, wherein the bed of fibers and resin matrixare suitable for fabricating composite structures when the resin matrixretains sufficient capacity for further curing that a compositestructure incorporating the prepreg composition can satisfy a selectedquality control standard.
 13. The composition of claim 1, wherein thebed of fibers and resin matrix are suitable for fabricating compositestructures until the resin matrix fails to exhibit adequate flow duringautoclaving.
 14. The composition of claim 13, wherein adequate flow is aselected value of a quantified resin flow characteristic as measured bya standard test method.
 15. A method of manufacturing a prepregcomposition, comprising: forming a bed of fibers; contacting the fiberbed with a resin matrix, wherein the bed of fibers and resin matrix aresuitable for fabricating composite structures until the bed of fibersand resin matrix are exposed to a threshold amount of UV radiation; anddisposing a plurality of core/shell quantum dots on or in the resinmatrix, an inner core of each quantum dot being configured to emit aluminescent signal when excited by light, and an outer shell beingconfigured to block light from reaching the inner core when the outershell is intact; wherein the plurality of core/shell quantum dots areconfigured such that exposure of the bed of fibers and resin matrix tothe threshold amount of UV radiation results in emission of theluminescent signal when the plurality of core/shell quantum dots isilluminated.
 16. The method of claim 1, wherein the inner core of eachquantum dot is configured such that when excited by light of a firstwavelength the inner core emits the luminescent signal at a secondwavelength; and the outer shell of each quantum dot is furtherconfigured such that exposure to the threshold amount of UV radiationresults in sufficient degradation that the inner core emits theluminescent signal when the quantum dot is illuminated by light havingthe first wavelength.
 17. The method of claim 1, wherein contacting thefiber bed with a resin matrix includes contacting the fiber bed with athermoset resin.
 18. The method of claim 1, wherein the plurality ofcore/shell quantum dots are disposed on or in the resin matrix beforethe resin matrix contacts the fiber bed.
 19. The method of claim 1,wherein the plurality of core/shell quantum dots are disposed on or inthe resin matrix after the resin matrix contacts the fiber bed.